Process for bleaching textiles

ABSTRACT

A process for bleaching textiles which comprises treating stained textiles in an aqueous bath containing at least one water-soluble aluminium phthalocyanine, under irradiation with light and in the presence of oxygen, while either irradiating the bleaching bath direct or subsequently irradiating the moist textiles outside the bath, as well as water-soluble aluminium phthalocyanines containing detergent compositions are described.

The present invention relates to a process for bleaching textiles, inparticular for bleaching textiles in a washing process, as well as todetergent and bleaching compositions for carrying out said process.

In conventional household laundry processes for white goods, such as bedlinen, table linen and white cotton goods, the articles are subjected toa combined washing and bleaching process in which the articles aretreated in an aqueous bath containing an organic detergent and ableaching agent. Other conventional detergent aids, such as alkalinebuilders, for example sodium tripolyphosphate, soil suspending agents,for example carboxymethyl cellulose, and fluorescent brightening agents,may also be present. The bleaching agent is usually a "per" compoundwhich releases oxygen at the wash temperature. Sodium perborate is thesubstance normally used for this purpose. In many cases, the bleaching(i.e., stain-removing) procedure can be carried out as a separate stepusing a compound which liberates chlorine, such as sodium hypochlorite,or N-chloro organic compounds, such as dichlorocyanuric acid or itssalts, or trichlorocyanuric acid.

These strain removal processes, however, result in varying degrees ofdegradation of the textile fibres. In addition, it is necessary to applyspecific temperatures in order to obtain useful effects, for exampletemperatures in excess of 75° C. when using sodium perborate.

Another process for removing stains from textiles is known from U.S.Pat. No. 3,927,967 and is based on an oxidation reaction which isphotoactivated by sulphonated zinc phthalocyanine.

The surprising discovery has now been made that stains can also beremoved from textiles by using, instead of sulphonated zincphthalocyanine, ecologically more advantageous water-soluble aluminiumphthalocyanines and that with these latter compounds an even moreadvantageous stain-removing effect is attained.

The process of the present invention for removing stains from textileswith photoactivating compounds comprises treating stained textiles in anaqueous bath containing at least one photoactivator selected from theclass of the water-soluble aluminium phthalocyanines, under irradiationwith visible and/or infra-red light and in the presence of oxygen, whileeither irradiating the bleaching bath direct or subsequently irradiatingthe moist textiles outside the bath.

The necessary water-solubility of the aluminium phthalocyanines suitablefor use as photoactivators in the process of the present invention canbe brought about by a wide variety of water-solubilising substituents.Such substituents are known from the literature relating tophthalocyanine dyes, especially copper and nickel phthalocyaninecomplexes. The water-solubility of an aluminium phthalocyaninederivative is sufficient when enough of it goes into solution in orderto effect a photodynamic catalysed oxidation on the fibre. A minimumsolubility of as little as 0.01 g/l can be sufficient; but in general asolubility of 0.1 to 20 g/l is advantageous. A number of possiblewater-solubilising groups are listed hereinafter, although thisenumeration makes no claim to be exhaustive. Sulpho and carboxyl groupsand the salts thereof as well as groups of the formulae

    __________________________________________________________________________     ##STR1##       (1),                                                                               ##STR2##       (1a),                                      ##STR3##       (1b),                                                                              ##STR4##       (2),                                       ##STR5##       (3),                                                                              SO.sub.2 (CH.sub.2).sub.nOSO.sub.3 M                                                          (4),                                      SO.sub.2 (CH.sub.2).sub.nSO.sub.3 M                                                           (4a),                                                                              ##STR6##       (5),                                       ##STR7##       (6),                                                                               ##STR8##       (7),                                       ##STR9##       (8),                                                                               ##STR10##      (9),                                       ##STR11##      (10),                                                                              ##STR12##      (10a),                                     ##STR13##      (11) or                                                                            ##STR14##      (12),                                 

wherein

X₁ represents oxygen, the radical --NH-- or --N-alkyl, and

R₁ and R₂, each independently of the other, represent hydrogen, thesulpho group and the salts thereof, the carboxyl group and the saltsthereof or the hydroxyl group, whilst at least one of the symbols R₁ andR₂ represents a sulpho or carboxyl group or the salts thereof,

Y₁ represents oxygen, sulphur, the radical --NH or --N-alkyl,

R₃ and R₄, each independently of the other, represent hydrogen, alkyl,hydroxyalkyl, cyanoalkyl, sulphoalkyl, carboxyalkyl or halogenalkyl eachcontaining 1 to 6 carbon atoms, phenyl which is unsubstituted orsubstituted by halogen, alkyl or alkoxy of 1 to 4 carbon atoms, sulphoor carboxyl, or R³ and R⁴ together with the nitrogen atom to which theyare attached form a saturated 5- or 6-membered heterocyclic ring whichcan additionally contain a further nitrogen or oxygen atom as ringmember,

R⁵ and R⁶, each independently of the other, represent a substituted orunsubstituted alkyl or aralkyl radical,

R₇ represents a substituted or unsubstituted alkyl group of 1 to 6carbon atoms or hydrogen,

M represents an alkali metal or ammonium ion,

Z.sup.⊖ represents an anion, for example a chlorine, bromine, alkyl orarylsulphate ion,

n is an integer from 2 to 12, and

m is 0 or 1.

In the above formulae, X₁ and Y₁ preferably represent --NH-- or--N-alkyl. Halogen preferably represents chlorine or bromine, especiallychlorine. Preferred 5- or 6-membered heterocyclic rings (R₃ +R⁴) are themorpholine, piperidine, pyrazoline, piperazine and oxazolidine radical.

The number of substituents present in the molecule is determined by asufficient water-solubility being attained. If severalwater-solubilising groups are present in the molecule, these can be thesame or different. As is customary in phthalocyanine chemistry, thedegree of substitution need not absolutely be a whole number, becauseproducts which are not always homogeneous result from the method ofmanufacture, for example sulphonation.

In addition to the water-solubilising groups, the aluminiumphthalocyanines suitable for use in the present invention can alsocontain other substituents, for example reactive radicals customary incolour chemistry, such as chloropyrazine, chloropyrimidine and, inparticular, chlorotriazine radicals.

The process of the invention can be carried out especiallyadvantageously by using as photoactivator a water-soluble aluminiumphthalocyanine of the formula

    AlX(PC)--(R).sub.v                                         ( 13)

wherein

Pc--represents the phthalocyanine ring system,

v--has any value between 1 and 4,

X--represents an anion, preferably a halide, sulphate, nitrate, acetateor hydroxyl ion, and

R--represents a group of the formula

    __________________________________________________________________________    SO.sub.3 Y      (14) ,                                                                              ##STR15##       (15) ,                                   ##STR16##      (16) ,                                                                              ##STR17##       (17)                                                    or                                                                                  ##STR18##       (18)                                

wherein

Y--represents hydrogen, an alkali metal, ammonium or amine ion,

R₇ '--represents hydrogen or alkyl of 1 to 4 carbon atoms,

n'--is an integer from 2 to 6,

R₁ and R₂, each independently of the other, represent hydrogen, thesulpho group and the salts thereof, the carboxyl group and the saltsthereof, whilst at least one of the symbols R₁ and R₂ represents asulpho or carboxyl group or the salts thereof, and

R₃ and R₄, each independently of the other, represent hydrogen, alkyl,hydroxyalkyl, cyanoalkyl, sulphoalkyl, carboxyalkyl or halogenalkyl,each containing 1 to 6 carbon atoms, or phenyl, or R₃ and R₄ togetherwith the nitrogen atom to which they are attached form a saturated 5- or6-membered heterocyclic ring which additionally can also contain afurther nitrogen or oxygen atom as ring member, with the proviso that,if several radicals R are present in the molecule, these radicals can beidentical or different, and that all radicals R are bonded to the phenylnuclei of the phthalocyanine ring system.

The nature of the anion X is of no importance for the action of thealuminium phthalocyanines. The purpose of this anion is solely tosaturate the third valency of the aluminium ion and is normallyidentical with the anion of the aluminium compound which has been usedfor the preparation of the complex.

Very effective removal of stains is obtained by the process of thepresent invention by using water-soluble aluminium phthalocyaninecompounds of the formula ##STR19## wherein PC and X are as defined informula (13),

n' is an integer between 2 and 6,

R₃ ' and R₄ ', each independently of the other, represent hydrogen,alkyl, hydroxyalkyl, cyanoalkyl or halogenalkyl, each containing 1 to 6carbon atoms, and v is an integer between 1 and 4, with the privisothat, if v is greater than 1, the radicals ##STR20## present in themolecule can be the same or different, or by using those of the formula##STR21## wherein PC and X are as defined in formula (13),

Y'--represents hydrogen, an alkali metal or ammonium ion,

n'--is an integer between 2 and 6,

R₃ ' and R₄ ', each independently of the other, represent hydrogen,phenyl, sulphophenyl, carboxyphenyl, alkyl, hydroxyalkyl, cyanoalkyl,sulphoalkyl, carboxyalkyl or halogenalkyl, each alkyl radical containing1 to 6 carbon atoms, or R₃ ' and R₄ ' together with the nitrogen atom towhich they are attached form the morpholine ring,

m--is 0 or 1, and

w and w₁, each independently of the other, is any number between 0.5 and3, whilst w+w₁ is at least 1, but not more than 4.

Particularly preferred photoactivators for use in the process of thepresent invention are sulphonated aluminium phthalocyanines, especiallythose of the formula

    AlX(PC--(SO.sub.3 Y').sub.v'                               ( 21)

wherein

Pc--represents the phthalocyanine ring system,

X--represents an anion, especially a halide, sulphate, hydroxyl oracetate ion,

Y'--represents hydrogen, an alkali metal or ammonium ion, and

v'--represents any number between 1.3 and 4 (degree of sulphonation).

Particularly good results are obtained with those compounds of theformula (21) in which the degree of sulphonation v' is 1.5 to 2.5, asthese compounds exhaust very well onto the fibres. Compounds havingdegrees of sulphonation of 2.5 to 4 also have good bleaching action.

As stated at the outset, the water-soluble, especially sulphonated,aluminium phthalocyanine complexes suitable for use in the process ofthis invention exhibit surprisingly excellent photodynamic effects,although this characteristic was not to be expected from the nature ofthe central atom. Whereas, for example, zinc complexes are known tocause photocatalytic reactions, these reactions are not really to beexpected of aluminium complexes. Moreover, compared with thecorresponding sulphonated zinc phthalocyanines (cf. U.S. Pat. No.3,927,967), the water-soluble aluminium phthalocyanine complexes used inthe present invention exhibit a higher light stability in solution aswell as better lightfastness properties on the fabric, wherebysubstantially smaller amounts of photoactivators can be used for a givendegree of bleaching. Furthermore, depending on the substitution, it ispossible to obtain high degrees of exhaustion onto the respectivefabric. Finally, from the ecological point of view, the use of aluminiumcomplexes is for known reasons to be preferred to that of zinc complexes(cf. Chemie in unserer Zeit 4 [1973], 97-105).

Even if the use of water-soluble aluminium phthalocyanines yields thebest results, the process of the invention can also be carried out if,instead of the aluminium complexes, calcium, magnesium or iron(II)complexes are used. Although good stain removal is also obtained withthese latter, compared with the aluminium complexes they have thedrawback of being less stable in aqueous solutions and under irradiationby light. In principle, however, the complexes of the above three metalscan be used in the process of the present invention as photoactivatorswith substituted phthalocyanine derivatives described above.

The corresponding alkali metal complexes also have a stain-removingaction, but are of less practical importance on account of their beingless stable in solution.

The bleaching process of the present invention, i.e., the treatment oftextiles with the photoactivator, is preferably carried out in a neutralor alkaline pH range.

The water-soluble phthalocyanines are advantageously used in amounts of0.01 to 100, especially 0.1 to 50, mg/l of the treatment bath. Theamount can vary greatly with the substitution of the phthalocyanines.

The process is preferably carried out as a combined washing andbleaching process, in which case the aqueous bath also contains anorganic detergent, such as soap or a synthetic detergent (see below),and can also contain other detergent aids, such as soil suspendingagents, for example sodium carboxymethyl cellulose, and fluorescentbrightening agents. The photoactivator can therefore either be alreadyincorporated in the corresponding detergent or can be added subsequentlyto the wash liquor. However, the process can also be carried out as apure stain-removing process without detergent aids. In this case, it isadvantageous if the treatment bath contains an electrolyte, for examplesodium chloride, sodium sulphate or sodium tripolyphosphate, in order toensure the exhaustion of the water-soluble aluminium phthalocyanine dye.The amounts of electrolyte can be about 5 to 20 g/l.

The stain-removing process is advantageously carried out at temperaturesin the range between about 20° and 100°, especially 20° and 85° C., overa period of 15 minutes to 5 hours, preferably 15 minutes to 60 minutes.

The presence of oxygen and irradiation with light in the visible and/orinfra-red range is necessary for the stain-removing process of theinvention. The oxygen dissolved in water or atmospheric oxygen sufficesas oxygen source.

The irradiation can be effected with an artificial light source whichaffords light in the visible and/or infra-red range (e.g. incandescentlamp, infra-red lamp), and the bleach or washing bath can be irradiateddirect, whether by means of a light source inside the receptaclecontaining the liquor (e.g. lamp in the washing machine) or by a lightsource outside the receptacle. Likewise, the irradiation can be effectedonly when the textiles are removed from the treatment bath. In thiscase, the textiles should however still be moist and, if not, they mustsubsequently be moistened again. Sunlight can also serve as lightsource, in which case the textiles are preferably exposed to sunlight inthe moist state after the treatment in the washing or bleach bath.

Although it is not possible to be bound by theory, it is nonethelessassumed that the mechanism of the stain-removing process takes thefollowing course: first the photoactivator (sens) absorbs light to raiseit to the triplet state

    .sup.1 sens+hν→.sup.3 sens.

This reacts with triplet oxygen to form singlet oxygen

    .sup.3 O.sub.2 +.sup.3 sens→.sup.1 O.sub.2 +.sup.1 sens

The singlet oxygen oxidises the stain to form colourless orwater-soluble oxidation products

    .sup.1 O.sub.2 +stain→stain O.sub.2.

such a theory is suggested for the photoactivated oxidation of organiccompounds by Foote and Wexler, J.A.C.S. 86, 3880 (1964).

The present invention also provides a detergent composition which issuitable for use in the process and which contains the customaryingredients of detergent and cleansing compositions, at least onebuilder salt and a photoactivator selected from the above mentionedgroup.

Suitable detergents are the known mixtures of active detergents, forexample soap in the form of chips and powders, synthetics, soluble saltsof sulphonic acid hemiesters of higher fatty alcohols, arylsulphonicacids with higher and/or multiple alkyl substituents, sulphocarboxylicacid esters of medium to higher alcohols, fatty acid acylaminoalkyl- oracylaminoaryl-glycerol sulphonates and phosphoric acid esters of fattyalcohols. Suitable builders which can be used are, for example, alkalimetal polyphosphates and polymetaphosphates, alkali metalpyrophosphates, alkali metal salts of carboxymethylcellulose and othersoil redeposition inhibitors, and also alkali metal silicates, alkalimetal carbonates, alkali metal borates, alkali metal perborates,nitrilotriacetic acid, ethylenediaminetetraacetic acid, and foamstabilisers, such as alkanolamides of higher fatty acids. The detergentscan further contain for example: antistatic agents, fat restorative skinprotectives, such as lanolin, enzymes, antimicrobial agents, perfumesand optical brighteners.

The detergent compositions of the present invention contain thephotoactivator preferably in an amount of 0.0005 to 1.25 percent byweight of the total composition. The preferred photoactivator is asulphonated aluminium phthalocyanine, for example one having a degree ofsulphonation of 1.5 to 4, especially 1.5 to 3.

The phthalocyanine compounds used in the process of the presentinvention can be prepared by methods which are known per se inphthalocyanine chemistry.

To introduce water-solubilising substituents, a start can be made fromunsubstituted phthalocyanine or its metal complexes. Sulphonation (e.g.with 26% oleum) results in the corresponding sulphonic acids, whereupon,depending on the duration of the sulphonation and on the temperature,products having a different degree of sulphonation are formed.Sulphonation of unsubstituted phthalocyanine yields for example at 45°to 60° C. disulphonic acid. The conversion into salts can beaccomplished in known manner.

Reaction of unsubstituted metal-free or metallised phthalocyanines withchlorosulphonic acid yields the corresponding sulphochloride compounds.Reaction of the resulting sulphochloride-phthalocyanines withcorrespondingly substituted aliphatic or aromatic amines or alcohols orphenols yields the phthalocyanines substituted by sulphonamide orsulphonic acid ester groups of the formulae (1), (1a), (5), (6) or (8,m=1). Saponification of the sulphochloride compounds yields thecorresponding sulphonic acids.

Carboxyl groups can be introduced into the unsubstituted phthalocyaninesby reaction with phosgene and aluminium chloride and hydrolysis of theresulting acid chloride or by reaction with trichloroacetic acid. Theacid chlorides can also be converted in known manner into otherwater-soluble carboxylic acid derivatives. Mixed substituted products(sulpho and carboxyl groups) can be obtained by a suitable combinationof the described processes. Phalocyanines substituted by carboxyl groupscan also be prepared by synthesis from trimetallitic acid.

Phthalocyanines which are substituted by groups of the formulae (2), (7)or (9), can be obtained by chloromethylation of unsubstituted metalfreeor metallised phthalocyanines, for example by reaction withparaformaldehyde or bis-chloromethyl ether and anhydrous aluminiumchloride in the presence of triethylamine, and subsequent reaction ofthe chloromethyl compounds with correspondingly substituted anilines,phenols or thiophenols or amines, alcohols or mercaptans. The reactionof the above chloromethyl intermediates with pyridine,1,4-diazabicyclo-[2,2,2]octane or with correspondingly unsubstituted orsubstituted tetraalkylthioureas yields phthalocyanines which aresubstituted by groups of the formulae (10, m=1), (10a) and (12, m=1).The above chloromethyl compounds can also be reacted with substituted orunsubstituted alkylsulphides to give the corresponding alkylthiomethylcompounds, and the latter with strong alkylating agents to givephthalocyanines which contain ternary groups of the formula (11, m=1).

Phthalocyanines which contain groups of the formulae (10, 11 or 12,m=0), can be prepared from the corresponding chlorine-substitutedphthalocyanines which are obtainable by direct chlorination of theunsubstituted phthalocyanines by the methods described for the reactionof chloromethyl compounds. Phthalocyanines which are substituted bywater-solubilising groups of the formulae (3) or (8, m=0) can also beobtained for example by starting from correspondingly substitutedphthalic anhydride or phthalodinitrile and reacting this latter compoundto give the phthalocyanine ring system. When using substitutedphthalodinitrile, this compound, optionally together with a metal salt,is fused or cyclised in solution or suspension to give thephthalocyanine ring system. When using the corresponding phthalicanhydride, urea and, if appropriate, a catalyst, for example boric acidor ammonium molybdate, is additionally added before the reaction. Othersubstituted phthalocyanines, for example the sulphonatedphthalocyanines, can also be obtained in this manner.

If the above described substitution reactions are not carried out directwith the aluminium phthalocyanine complex, or the syntheses of thephthalocyanine ring system are not carried out in the presence of analuminium compound, a correspondingly substituted metal-freephthalocyanine can be reacted subsequently with an aluminium salt oraluminium alcoholate in a solvent. Suitable solvents are for examplemixtures of water and organic solvents, especially also tertiary aminesor also anhydrous organic solvents, for example pyridine orchlorobenzenes. This mode of manufacture is also especially advantageousfor more easily hydrolysable complexes, such as the alkali metal,alkaline earth metal and iron(II) complexes.

It will be understood that the correspondingly substituted aluminiumphthalocyanine complexes can also be obtained from other metal complexesby substituting aluminium for the respective metal.

In the following Examples, which illustrate the manufacture of thephotoactivators of the present invention as well as the process of theinvention itself, all percentages are by weight. In all Examples, theabbreviation PC denotes the unsubstituted phthalocyanine.

EXAMPLE 1

2.66 g of aluminium chloride are added to a solution of 6.76 g ofphthalocyanine-disulphonic acid having an absorption maximum of 612 nmin a buffer solution of pH 7 (0.01 mole/l of sodium hydrogenphosphate/0.007 mole/l of potassium hydrogen phosphate) in 500 ml of a1:1 mixture of pyridine/water. The solution is refluxed for 2 hours andthen concentrated by rotary evaporation. The residue is taken up in 75ml of water and the solution neutralised with ammonia, yielding thedisulphonated aluminium phthalocyanine with an absorption maximum of 675nm (buffer solution of pH 7).

The corresponding phthalocyanines listed in Table 1 are obtained byrepeating the procedure described in this Example, but using salts ofother metals.

                  Table 1                                                         ______________________________________                                                                    λ max.                                                                 in H.sub.2 O, pH9                                 metal salt                                                                             Phthalocyanine derivative                                                                        (nm)                                              ______________________________________                                        Mg Cl.sub.2                                                                            Mg (PC)(SO.sub.3 H).sub.2                                                                        669                                               Ca Cl.sub.2                                                                            Ca (PC)(SO.sub.3 H).sub.2                                                                        653                                               Fe SO.sub.4                                                                            Fe (PC)(SO.sub.3 H).sub.2                                                                        662                                               ______________________________________                                    

EXAMPLE 2

(a) 52.5 g of phthalic anhydride, 64 g of urea, 1 g of ammoniummolybdate, 27 g of sodium m-xylenesulphonate are stirred in 175 g oftrichlorobenzene and mixed with a suspension of 15 g of anhydrousaluminium chloride in 25 g of trichlorobenzene. After stirring for 6hours at 200° to 205° C., 27 g of urea and 50 g of trichlorobenzene areadded and stirring is continued for a further 5 hours at the sametemperature. The suspension is filtered cold and the residue is washedwith chlorobenzene and with methanol and then purified by extraction byboiling in dilute hydrochloric acid, dilute sodium hydroxide solutionand again in dilute hydrochloric acid, then dired, affording 34 g of analuminium phthalocyanine whose analysis corresponds to the formula

    C.sub.32 H.sub.16 N.sub.8 AlCl.2 H.sub.2 O.

(b) 20 g of this aluminium phthalocyanine are stirred in 220 ml of 30%oleum for 8 hours at 73°-75° C. After cooling to room temperature, theresulting solution is poured onto ice and 10% sodium chloride solution.The suspension is filtered and the residue is washed with a 10% sodiumchloride solution and 1 N hydrochloric acid and dried in vacuo at 90° C.

Yield: 22 g. The product has the formula

    AlCl(PC) (SO.sub.3 H).sub.2                                (201)

    λmax=671 nm (in H.sub.2 O, pH 9).

in (a), it is also possible to use any other aluminium salt instead ofaluminium chloride. Depending on the nature of the anion, in thisExample and in those which follow, aluminium phthalocyanine derivativesare obtained in which the third valency of aluminium is saturated withany other anion (e.g. sulphate, acetate, hydroxyl etc.) instead of withchlorine.

EXAMPLE 3

(a) 20 g of the aluminium phthalocyanine prepared in accordance withExample 2(a) are added to 140 ml of chlorosulphonic acid at 20°-25° C.and the mixture is stirred for 30 minutes. The temperature is thenraised to 135°-140° C. in the course of 2 hours. After stirring for 4hours, the reaction mixture is cooled to room temperature and pouredonto ice. The suspension is filtered and the residue is washed free ofacid with ice-water.

(b) The moist filter cake is stirred in 500 ml of ice-water and then 3.2g of ethanolamine are added. With stirring, the pH is kept at 8 to 9 byaddition of 10% sodium hydroxide solution. After stirring for 2 hours at0° to 25° C., the temperature is raised to 60°-70° C. and kept thereatfor 5 hours. The product is precipitated completely by addition ofsodium chloride, collected by filtration and dried in vacuo at 70° to80° C. The resulting compound has the formula ##STR22##

    λmax=677,5 nm (in H.sub.2 O, pH 7).

the compounds of the general formula ##STR23##

listed in Table 2 are obtained by reacting the aluminium phthalocyaninetetrasulphochloride obtained by the procedure of Example 3(a) inanalogous manner with other amines.

                                      Table 2                                     __________________________________________________________________________    For-                                                                          mula                                                                             R                          x  Amine                                        __________________________________________________________________________    303                                                                              NH.sub.2                   1  NH.sub.4 OH                                  304                                                                              NHCH.sub.3                 1  H.sub.2 NCH.sub.3                            305                                                                              N(CH.sub.2 CH.sub.2 OH).sub.2                                                                            1.5                                                                              HN(CH.sub.2 CH.sub.2 OH).sub.2               306                                                                              NHCH.sub.2 CH.sub.2 N(CH.sub.3).sub.2                                                                    3  H.sub.2 NCH.sub.2 CH.sub.2 N(CH.sub.3).su                                     b.2                                          307                                                                              NHCH.sub.2 CH.sub.2 CH.sub.2 N(CH.sub.3).sub.2                                                           4  H.sub.2 NCH.sub.2 CH.sub.2 CH.sub.2                                           N(CH.sub.3).sub.2                            308                                                                               ##STR24##                 2                                                                                 ##STR25##                                   309                                                                              NHCH.sub.2 CH.sub.2 OSO.sub.3 H                                                                          2  H.sub.2 NCH.sub.2 CH.sub.2 OSO.sub.3 H       310                                                                              NH(CH.sub.2).sub.6 COOH    1  H.sub.2 N(CH.sub.2).sub.6 COOH               311                                                                               ##STR26##                 1                                                                                 ##STR27##                                   312                                                                               ##STR28##                 1.5                                                                               ##STR29##                                   313                                                                               ##STR30##                 1                                                                                 ##STR31##                                   314                                                                               ##STR32##                 1                                                                                 ##STR33##                                   315                                                                               ##STR34##                 2                                                                                 ##STR35##                                   316                                                                               ##STR36##                 1                                                                                 ##STR37##                               

EXAMPLE 4

20 g of the aluminium phthalocyanine tetrasulphochloride obtained by theprocedure of Example 3(a) are added to 500 ml of water and hydrolysed byaddition of sodium hydroxide solution at 60°-70° C. After concentratingto dryness, 25 g of aluminium phthalocyanine tetrasulphonic acid (sodiumsalt) of the formula

    AlCl(PC) (SO.sub.3 Na).sub.4                               (401)

    λmax=672,75 nm (in H.sub.2 O, pH 9).

are obtained.

The same compound can also be obtained by sulphonation of theunsubstituted aluminium phthalocyanine (obtainable by the procedure ofExample 2(a) with 60% oleum at 70°-75° C.

EXAMPLE 5

(a) 20 g of the aluminium phthalocyanine prepared by the procedure ofExample 2(a) are added at 25° C. to 150 ml of chlorosulphonic acid andthe mixture is stirred for 30 minutes. The reaction mixture is thenheated to 65°-70° C. and 32 ml of thionyl chloride are added dropwise inthe course of 20 minutes. The temperature is subsequently raised to110°-115° C. in the course of 2 hours and kept thereat for 6 hours.After cooling to 25° C., the reaction mass is poured onto ice such thatthe temperature does not rise above 0° C. in doing so. The suspension isfiltered and the residue is washed free of acid with ice-water.

(b) The moist filter cake, consisting of aluminium phthalocyaninetrisulphochloride, is stirred in 500 ml of ice-water and then 32 g of1-amino-3-dimethylaminopropane are added. After stirring for 15 hours at20°-30° C., the temperature is raised for a further 4 hours to 60°-70°C. The suspension is filtered, and the residue is washed with warm waterand dried in vacuo at 70°-80° C., affording the compound of the formula

    AlCl(PC)-[SO.sub.2 NHCH.sub.2 CH.sub.2 CH.sub.2 N(CH.sub.3).sub.2 ].sub.3 ( 501)

    λmax=675,5 nm (in H.sub.2 O, pH 7).

in analogous manner, the compounds of the formula

    AlCl(PC)-[SO.sub.2 --R].sub.3                              (502)

listed in Table 3 can be obtained by reaction of aluminiumtrisulphochloride, obtained by the procedure of Example 5(a), with acorresponding amine.

    ______________________________________                                        For-                   Starting compound                                      mula       R             HR                                                   ______________________________________                                        503  NHCH.sub.2 CH.sub.2N(CH.sub.3).sub.2                                                            H.sub.2 NCH.sub.2 CH.sub.2N(CH.sub.3).sub.2            504                                                                                 ##STR38##                                                                                       ##STR39##                                             ______________________________________                                    

example 6

20 g of the aluminium phthalocyanine prepared by the procedure ofExample 2(a) are added at 25° C. to 220 ml of 25% oleum and the mixtureis stirred for 7 hours at 40° C. After stirring for a further 12 hoursat room temperature, the mass is poured into a mixture of ice/sodiumchloride, filtered and washed with 500 ml of 5% hydrochloric acid. Thefilter residue is dried in vacuo at 70° C.

The product has the formula

    AlCl(PC) (SO.sub.3 H).sub.1,4                              (601)

    λmax=676 nm (in H.sub.2 O, pH 10).

example 7

20 g of the aluminium phthalocyanine obtained by the procedure ofExample 2(a) are stirred in 240 ml of 33% oleum for 7 hours at 73°-75°C. The reaction mixture, which has been cooled to 25° C., is chargedinto a mixture of 1000 g of ice and 200 g of sodium chloride. Thetemperature is kept at 0° to 20° by further addition of ice. Thesuspension is filtered and the filter residue is washed neutral with a10% sodium chloride solution, then with 300 ml of 10% hydrochloric acid.The product is dried at 80° C. in vacuo. The resulting product has theformula

    AlCl(PC) (SO.sub.3 H).sub.3                                (701)

    λmax=671 nm (in H.sub.2 O, pH 9).

carrying out the above sulphonation with 40% oleum yields a product ofthe formula

    AlCl(PC) (SO.sub.3 H).sub.<4                               (702)

    λmax=671,75 (in H.sub.2 O, pH 9).

example 8

a cotton fabric weighing 1 g and stained with tea (*) is treated at 55°C. under irradiation with a 200 watt incandescent lamp (**) for 1 hourwith stirring in 200 ml of an aqueous wash liquor which contains 0.75ppm of aluminium phthalocyanine-disulphonic acid (prepared in accordancewith Example 1) and 1 g of a detergent of the following composition:

    ______________________________________                                        sodium dodecylbenzenesulphonate                                                                        16%                                                  sodium tripolyphosphate  43%                                                  sodium silicate          4%                                                   magnesium silicate       2%                                                   fatty alcohol sulphonate 4%                                                   sodium carboxymethyl cellulose                                                                         1%                                                   sodium salt of ethylenediamine-                                               tetraacetic acid         0.5%                                                 sodium sulphate          29.5%                                                ______________________________________                                    

The degree of stain removal is measured with a Zeiss Elrepho®-Photometer(standard illuminant D65, 2 degree normal viewer, measuring diaphragm 35mm φ) in the form of brightness values, expressed in %, based on theabsolute whiteness in accordance with the C.I.E. recommendation of1.1.1969. The values obtained are reported in Table 4.

                  Table 4                                                         ______________________________________                                                        Degree of stain removal                                                       (=brightness value, in %)                                     ______________________________________                                        tea-stained cotton                                                                              51.4                                                        stain removal wash with                                                        AlCl(PC)(SO.sub.3 H).sub.2                                                                     77.9                                                        ______________________________________                                    

(*) The staining of the cotton sample is carried out as follows: 15 g oftea ("Fine Ceylon Fannings Tea") are boiled for 1 hour in 600 ml ofdesalinated water and then filtered. The filtered tea leaves are takenup in 400 ml of desalinated water and boiled again for 60 minutes. Bothfiltrates are combined and made up to 1000 ml with desalinated water.With constant agitation, 45 g of cotton fabric (bleached and washed) aretreated at 100° C. for 21/2 hours, then "staining" is effected in acooled bath for a further 16 hours. Then 5 g of sodium chloride areadded to the tea liquor and treatment is carried out again for 21/2hours at 100° C. Finally, the liquor is cooled and the stained cotton isrinsed twice at 60° C. and dried at 100° C. Finally, the stained fabricis washed with a liquor containing 5 g/l of detergent (composition, seeabove), washed for 20 minutes at 90° C. (liquor ratio 1:20), rinsed warmand cold and dried at 100° C. in a forced draught oven. (**) Lamp:"Luxram" incandescent lamp of 220/230 volts, 200 watts, E 27, frosted.The lamp is mounted about 10 cm above the wash liquor. Measured lightintensity: 19,000 lux.

EXAMPLE 9

A cotton sample, weighing 1 g and coloured with a brown dye(*), istreated at 55° C. under irradiation with an infra-red lamp(**) for 1/2hour, with stirring, with 200 ml of an aqueous liquor containing 2 g ofsodium chloride, 0.06 g of sodium hydroxide and 1 ppm of aluminiumphthalocyanine-disulphonic acid. For comparison purposes, a similarcotton sample is treated with a liquor of the same composition whichcontains, instead of 1 ppm of aluminium phthalocyanine-disulphonic acid,the same amount of zinc phthalocyanine-disulphonic acid.

After the treatment, the samples are rinsed and dried. The amount ofbrown dye adhering to the respective fabric samples and of thephthalocyanine compound is determined colorimetrically (results inpercent by weight, based on the weight of the sample, see Table 5).

                  Table 5                                                         ______________________________________                                                     Brown dye Phthalocyanine                                                      (%)       compound (%)                                           ______________________________________                                        unbleached     0.139       --                                                 bleached with  0.021       0.0037                                             AlCl(PC)(SO.sub.3 H).sub.2                                                    bleached with  0.02        decomposed                                         Zn(PC)(SO.sub.3 H).sub.2                                                      ______________________________________                                    

It follows from the measurements that AlCl(PC)(SO₃ H)₂ is decomposedless rapidly by the irradiation that Zn(PC)(SO₃ H)₂.

(*) The dyeing of the cotton sample is carried out as follows: 150 mg ofthe commercially available brown dye of the formula ##STR40## aredissolved in 2000 ml of water which contains 1 g of sodium carbonate ata temperature of 50° C. Bleached, mercerised cotton fabric (100 g) isdyed in this dye liquor, with constant agitation, by heating the bathfor 30 minutes to 90° C. Dyeing is carried out for 90 minutes, in thecourse of which time 20 g of Glauber's salt are added in 4 portions ofequal size at intervals of 15 minutes.

When the dyeing is complete, the fabric is rinsed cold twice andcoppered for 20 minutes at 60° C. in a liquor ratio of 1:20 in a bathcontaining 0.75 g/l of copper sulphate crystals and 1 ml/l of glacialacetic acid. The dyeing is subsequently rinsed cold twice and dried in ahot-air oven at 100° C.

(**) Lamp: "Phillips" infra-red lamp (white), 220/230 volts, 250 wattwith reflector, type 13372 E/06. The lamp is mounted about 10 cm abovethe liquor. Measured light intensity: 85,000 lux.

EXAMPLE 10

10 g of a cotton sample dyed in accordance with Example 9 with a browndye are put into 200 ml of water in which 0.75 mg of aluminiumphthalocyanine-disulphonic acid and 0.2 g of sodium tripolyphosphate aredissolved. With constant agitation, the liquor is heated to 75° C. andkept for 90 minutes at this temperature, while 4 g of Glauber's salt areadded in 4 portions of equal size at 10 minute intervals. Afterwards thefabric sample is rinsed cold briefly and dried in a forced draught ovenat 100° C. All previously described operations are carried out with thesubstantial exclusion of light.

For comparison purposes, a similar fabric sample is treated, using 1.2mg of zinc phthalocyanine-disulphonic acid instead of 0.75 mg ofaluminium phthalocyanine-disulphonic acid.

The coloured samples are then moistened with a buffer solution of pH 10(composition: 0.03 mole/l of disodium tetraborate and 0.042 mole/l ofsodium hydroxide) and exposed at room temperature under an overheadprojector (portable projector, Model 088/88 BH, available from 3M, witha lamp of type 78-8454/3480, General Electric, 240 volts, 480 watt).

The samples are under a glass plate at a spacing of 30 cm beneath thelamp. For control purposes, a piece of fabric dyed brown is also exposedin the same way without treatment with phthalocyanines.

To determine the brown dye decomposed during the exposure and the amountof phthalocyanine compounds remaining on the fabric, the samples areevaluated colorimetrically against standard dyeings. The values obtainedare reported in Table 6 (in percent by weight of dye, based on theweight of the fabric).

                                      Table 6                                     __________________________________________________________________________                   Brown dye                                                                              Brown dye                                             Dyeing   Brown dye                                                                           treated with                                                                           treated with                                                                            Amount of                                                                              Amount of                          Expose   alone Zn(PC)(SO.sub.3 H).sub.2                                                               AlCl(PC)(SO.sub.3 H).sub.2                                                              Zn(PC)(SO.sub.3 H).sub.2                                                               AlCl(PC)(SO.sub.3 H).sub.2         time     in (%)                                                                              in (%)   in (%)    in (%)   in (%)                             __________________________________________________________________________    before exposure                                                                        0.1519                                                                              0.1294   0.1291    0.0115   0.007                              30 min. exposure                                                                             0.0298   0.0345    0.0053   0.0066                             (%age of initial                                                                             (23.03%) (26.72%)  (46.08%) (94.29%)                           amount)                                                                       60 min. exposure                                                                       0.1263                                                                              0.0218   0.0186    0.0039   0.0062                             (%age of initial                                                                       (83.15%)                                                                            (16.85%) (14.41%)  (33.91%) (88.57%)                           amount)                                                                       120 min. exposure                                                                            0.0195   0.0137    0.0034   0.0059                             (%age of initial                                                                             (15.07%) (10.61%)  (29.57%) (84.29%)                           amount)                                                                       150 min. exposure                                                                      0.1199                                                                              0.0141   0.012     0.0030   0.0056                             (%age of initial                                                                       (78.94%)                                                                            (10.90%) (9.30%)   (26.00%) (80%)                              amount)                                                                       __________________________________________________________________________

The percentages in brackets refer to respective initial amounts beforethe exposure.

Cotton fabric stained with tea can also be bleached with equally goodsuccess by the process described in Example 10.

EXAMPLE 11

Pieces of cotton fabric dyed with brown dye in accordance with Example 9are washed at 55° C. for 60 minutes (liquor ratio 1:200), with stirringand under irradiation with a 200 watt standard incandescent lamp mountedat a distance of about 10 cm from the surface of the wash liquor, in awash liquor containing 2.5 g/l of sodium carbonate, 2.5 g/l of adetergent of the composition indicated in Example 8 and the respectiveamount of a water-soluble aluminium phthalocyanine given in Table 7.After washing, the fabric is rinsed, dried, and its brightness valuedetermined in the same way as indicated in Example 8. The brightnessvalues (in %) are also reported in Table 7.

                  Table 7                                                         ______________________________________                                        Water-soluble                                                                             amount added                                                      aluminium   (in ppm, based on                                                 phthalocyanine                                                                            the weight of the                                                                            brightness value                                   of the formula                                                                            fabric)        (%)                                                ______________________________________                                          201       0.75           78.1                                                 301       0.75           75.5                                                 401       7.5            73.1                                                 501       0.5            73.1                                                 601       0.5            75.3                                                 701       1.25           78.5                                                 702       5.0            78.6                                               Test fabric                                                                   washed without                                                                photoactivator                                                                            --             53.3                                               (brown coloura-                                                               tion)                                                                         ______________________________________                                    

Similarly good results are obtained with the compounds of the formulae(303) to (316) and (503) and (504).

EXAMPLE 12

In the same way as described in Example 11, the stain removal action ofthe water-soluble aluminium phthalocyanine derivatives of the generalformula

    AlCl(PC--[CH.sub.2 -R.sub.x ].sub.v                        (1201)

listed in Table 8 is also tested.

                  Table 8                                                         ______________________________________                                        Formula   R.sub.x               v                                             ______________________________________                                        1202                                                                                     ##STR41##            3                                             1203                                                                                     ##STR42##            3                                             1204                                                                                     ##STR43##            3                                             1205                                                                                     ##STR44##            2                                             1206                                                                                     ##STR45##            3                                             1207                                                                                     ##STR46##            3                                             ______________________________________                                    

The compounds listed in Table 8 also effect a very good stain removalaction.

The sulphonated calcium, magnesium and iron(II) phthalocyanines obtainedaccording to Example 1 are also investigated for their stain-removalaction by the method of Example 11 and exhibit likewise useful effects.

What is claimed is:
 1. A process for bleaching textiles with photoactivecompounds, which comprises treating stained textiles in an aqueous bathcontaining at least one photoactivator selected from the class of thewater-soluble aluminum phthalocyanines, under irradiation with visibleand/or infra-red light and in the presence of oxygen, while eitherirradiating the bleaching bath direct or subsequently irradiating themoist textiles outside the bath.
 2. A process as claimed in claim 1,wherein the photoactivator is an aluminum phthalocyanine which issubstituted by one or more water-solubilising groups selected from thegroup consisting of sulpho and carboxyl groups and the salts thereof,and groups of the formulae ##STR47## wherein X₁ represents oxygen, theradical --NH-- or --N-alkyl, andR₁ and R₂, each independently of theother, represent hydrogen, the sulpho group and the salts thereof, thecarboxyl group and the salts thereof or the hydroxyl group, whilst atleast one of the symbols R₁ and R₂ represents a sulpho or carboxyl groupor the salts thereof, Y₁ --represents oxygen, sulphur, the radical--NH-- or --N-alkyl, R₃ and R₄, each independently of the other,represent hydrogen, alkyl, hydroxyalkyl, cyanoalkyl, sulphoalkyl,carboxyalkyl or halogenalkyl, each containing 1 to 6 carbon atoms,phenyl which is unsubstituted or substituted by halogen, alkyl or alkoxyof 1 to 4 carbon atoms, sulpho or carboxyl, or R₃ and R₄ together withthe nitrogen atom to which they are attached form a saturated 5- or6-membered heterocyclic ring which can additionally contain a furthernitrogen or oxygen atom as ring member, R₅ and R₆, each independently ofthe other, represent a substituted or unsubstituted alkyl or aralkylradical, R₇ --represents a substituted or unsubstituted alkyl group of 1to 6 carbon atoms or hydrogen, M--represents an alkali metal or ammoniumion, Z.sup.⊖ --represents an anion selected from the group consisting ofchloride, bromide, alkylsulphate and arylsulphate ions, n--is an integerfrom 2 to 12, and m--is 0 or 1, and, in addition to thewater-solubilising groups, zero or more substituents selected from thegroup consisting of chlorotriazine, chloropyrazine and chloropyrimidineradicals.
 3. A process as claimed in claim 2, wherein the photoactivatoris a water-soluble aluminum phthalocyanine of the formula

    AlX(PC--(R).sub.v

wherein Pc--represents the phthalocyanine ring system, v--has any valuebetween 1 and 4, X--represents an anion, preferably a halide, sulphate,nitrate, acetate or hydroxyl ion, and R--represents a group of theformula ##STR48## wherein Y--represents hydrogen, an alkali metal,ammonium or amine ion, R₇ '--represents hydrogen or alkyl of 1 to 4carbon atoms, n'--is an integer from 2 to 6, R₁ and R₂, eachindependently of the other, represent hydrogen, the sulpho group and thesalts thereof, the carboxyl group and the salts thereof, whilst at leastone of the symbols R₁ and R₂ represents a sulpho or carboxyl group orthe salts thereof, and R₃ and R₄, each independently of the other,represent hydrogen, alkyl, hydroxyalkyl, cyanoalkyl, sulphoalkyl,carboxyalkyl or halogenalkyl, each containing 1 to 6 carbon atoms, orphenyl, or R₃ and R₄ together with the nitrogen atom to which they areattached form a saturated 5- or 6-membered heterocyclic ring whichadditionally can also contain a further nitrogen or oxygen atom as ringmember, with the proviso that, if several radicals R are present in themolecule, these radicals can be the same or different and all radicals Rare bonded to the phenyl nuclei of the phthalocyanine ring system.
 4. Aprocess as claimed in claim 3 which comprises the use of an aluminumphthalocyanine of the formula ##STR49## wherein PC and X are as definedin claim 3,n' is an integer between 2 and 6, R₃ ' and R₄ ', eachindependently of the other, represent hydrogen, alkyl, hydroxyalkyl,cyanoalkyl or halogenalkyl, each containing 1 to 6 carbon atoms, and vis an integer between 1 and 4,with the proviso that, if v is greaterthan 1, the radicals ##STR50## present in the molecule can be the sameor different.
 5. A process as claimed in claim 3 which comprises the useof a sulphonated aluminum phthalocyanine as water-solublephthalocyanine.
 6. A process as claimed in claim 5 which comprises theuse of a sulphonated aluminum phthalocyanine of the formula

    AlX(PC--(SO.sub.3 Y').sub.v'

wherein Pc--represents the phthalocyanine ring system, X--represents ananion selected from the group consisting of halide, sulphate, hydroxyland acetate ions, Y'--represents hydrogen, an alkali metal or ammoniumion, and v'--represents any number between 1.3 and 4 (degree ofsulphonation).
 7. A process as claimed in claim 6 which comprises theuse of a sulphonated aluminum phthalocyanine having a degree ofsulphonation of 1.5 to 2.5.
 8. A process as claimed in claim 6 whichcomprises the use of a sulphonated aluminum phthalocyanine having adegree of sulphonation of 2.5 to
 4. 9. A process as claimed in claim 3which comprises the use of a water-soluble phthalocyanine of the formula##STR51## wherein PC and X are as defined in claim 3,Y'--representshydrogen, an alkali metal or ammonium ion, n'--is an integer between 2and 6, R₃ ' and R₄ ', each independently of the other, representhydrogen, phenyl, sulphophenyl, carboxyphenyl, alkyl, hydroxyalkyl,cyanoalkyl, sulphoalkyl, carboxyalkyl or halogenalkyl, each alkylradical containing 1 to 6 carbon atoms, or R₃ ' and R₄ ' together withthe nitrogen atom to which they are attached form the morpholine ring,m--is 0 or 1, and w and w₁, each independently of the other, is anynumber between 0.5 and 3, whilst w+w₁ is at least 1, but not more than4.
 10. A process as claimed in claim 1, wherein the aqueous bathcontains an electrolyte in addition to the photoactivator.
 11. A processas claimed in claim 10, wherein sodium chloride, sodium sulphate orsodium tripolyphosphate is used as electrolyte.
 12. A process as claimedin claim 1 which comprises the use of an aqueous bath which alsocontains an organic detergent and, if desired, other conventionaldetergent ingredients.
 13. A process as claimed in claim 1, wherein thephotoactivator is present in a concentration of 0.1 to 50 mg/l of thebath.
 14. A process as claimed in claim 1, wherein the irradiation iscarried out with an artificial light source, preferably an incandescentlamp or infra-red lamp, either in the bleaching bath or outside thebleaching bath.
 15. A process as claimed in claim 1, wherein thetextiles are irradiated in sunlight.
 16. A process as claimed in claims1, 14 and 15, wherein the intensity of the visible light is at least1000 lumen.
 17. A process as claimed in claim 16, wherein the textilesare treated at a temperature between 10° and 85° C.
 18. A process asclaimed in claim 5, which comprises treating the textiles in an aqueousbath containing the phthalocyanine compound, removing the textiles fromthe bath and then, when they are still moist or have been moistenedagain after drying, irradiating the textiles with a suitable source ofartifical light or exposing them to sunlight.
 19. A detergentcomposition containing an organic detergent, an alkaline builder saltand a photoactivator selected from the class of the water-solublealuminum phthalocyanines.
 20. A detergent composition as claimed inclaim 19, which contains 0.0005 to 1.5 percent by weight ofphotoactivator, based on the entire composition.
 21. A detergentcomposition containing an organic detergent, an alkaline builder saltand 0.0005 to 1.5 percent by weight of a water-soluble aluminumphthalocyanine photoactivator of claim
 3. 22. A detergent composition asclaimed in claim 20, which contains sulphonated aluminum phthalocyanineas photoactivator.